Polyamines as aldehyde scavengers

Abstract

The present invention relates to a method for producing polyurethanes, the method comprising the steps of: (a) a polyisocyanate; (b) a polymeric compound having groups reactive towards isocyanates; (c) optionally a catalyst; (d) a compound of the general formula H 2 NW-NR-[W-NR] l -[Q-NR] m -[S-NR] n -W-NH 2 and optionally (e) a blowing agent, (f) a chain extender and / or crosslinker and (g) an auxiliary and / or additive to form a reaction mixture and reacting said reaction mixture to obtain a polyurethane, wherein each W independently of the others represents a linear or branched hydrocarbon having 3 to 10 carbon atoms, each Q represents an ethylene residue, each S independently of the others represents a substituted hydrocarbon, each R independently of the others represents hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms, H represents a hydrogen atom, and N represents a nitrogen atom, l represents a value of 0 to 100, m represents a value of 0 to 50 and n represents a value of 0 to 100, wherein the polydispersity of said polymeric amine (d) is at least 1.2. The invention further relates to polyurethanes which can be prepared by the process according to the invention, as well as the use of such polyurethanes in enclosed spaces, for example in vehicles, and to a method for producing polyurethanes comprising the steps of: (b) a polymeric compound having groups reactive towards isocyanates, (c) a catalyst and (d) a polymeric compound of the general formula H 2 NW-NR-[W-NR] l -[Q-NR] m -[S-NR] n -W-NH 2 and a blowing agent comprising water, wherein the polydispersity of said polymeric amine (d) is at least 1.2.

Description

[Technical field]

[0001] The present invention relates to a method for producing polyurethanes, the method comprising the steps of: (a) a polyisocyanate; (b) a polymeric compound having groups reactive towards isocyanates; (c) optionally a catalyst; (d) a compound of the general formula H 2 NW-NR-[W-NR] l -[Q-NR] m -[S-NR] n -W-NH 2 and optionally (e) a blowing agent, (f) a chain extender and / or crosslinker and (g) an auxiliary and / or additive to form a reaction mixture and reacting said reaction mixture to obtain a polyurethane, wherein each W independently of the others represents a linear or branched hydrocarbon having 3 to 10 carbon atoms, each Q represents an ethylene residue, each S independently of the others represents a substituted hydrocarbon, each R independently of the others represents hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms, H represents a hydrogen atom, and N represents a nitrogen atom, l represents a value of 0 to 100, m represents a value of 0 to 50 and n represents a value of 0 to 100, wherein the polydispersity of said polymeric amine (d) is at least 1.2. The invention further relates to polyurethanes which can be prepared by the process according to the invention, as well as the use of such polyurethanes in enclosed spaces, for example in vehicles, and to a method for producing polyurethanes comprising the steps of: (b) a polymeric compound having groups reactive towards isocyanates, (c) a catalyst and (d) a polymeric compound of the general formula H 2 NW-NR-[W-NR] l -[Q-NR] m -[S-NR] n -W-NH 2 and a blowing agent comprising water, wherein the polydispersity of said polymeric amine (d) is at least 1.2.

[0002] Polyurethanes are distinguished by their wide range of applications, for example in the furniture industry as seat cushioning materials or as binders for particleboards, in the construction industry as insulating materials, for example for pipes, hot water tanks or refrigerators, and for example in vehicle construction as panel components. In particular, in automobile construction, polyurethanes are often used, for example, in the exterior of automobiles as spoilers, roof elements, suspension elements, and in the interior of automobiles as roof panels, carpet foam backings, door panels, steering wheels, gear knobs and seat cushioning materials.

[0003] In this case, it is known that polyurethane tends to emit organic substances that can cause odor problems or ill health in high concentrations.In this case, particularly closed spaces, such as buildings or vehicle interiors, such as automobiles, are particularly affected.One example of such emission is the emission of aldehyde.In this case, there are already various approaches to reduce the amount of aldehyde emission.

[0004] For example, EP 1428847 describes that the aldehyde emission can be reduced by the subsequent addition of a polymeric substance having primary and / or secondary amino groups. The amino groups in the polymer are responsible for the reduction in the emission. Specifically described are polyvinylamine, polyethyleneimine and polyamidoamine. A disadvantage of using polyvinylamine is, for example, that this substance, due to its manufacturing method, may contain impurities that cause corrosion of containers and equipment. Polyethyleneimine does indeed act as a formaldehyde scavenger, but it leads to an increase in acetaldehyde emission.

[0005] US 20130203880 describes the use of polyhydrazodicarbonamide as a substance for reducing aldehyde emissions in polyurethane foams. However, a clear reduction in aldehydes is only achieved when adding large amounts of polyhydrazodicarbonamide, from 2 to 5.5% by weight in the polyol component. Since polyhydrazodicarbonamide also has catalytic properties, the addition of this amount of this substance changes the reaction profile. Furthermore, the aldehyde reduction achieved when using large amounts of polyhydrazodicarbonamide itself needs to be further improved.

[0006] WO 2015082316 describes a compound of the general formula R for reducing formaldehyde emissions in combination with an incorpo- rable catalyst. 1 -CH 2 -R 2 [In the formula, R 1 and R 2 The use of CH acidic compounds of the formula [wherein independently represent electron-withdrawing residues] is described, which can effectively reduce formaldehyde, however the foam specimens still show high emissions of volatile organic substances (VOCs).

[0007] EP 3310824 describes a method for producing polyurethanes by reacting polyisocyanates and polyols in the presence of aldehyde scavengers selected from 1-benzyl-1,3-propanediamine, isotridecyloxypropyl-1,3-diaminopropane, dodecyloxypropyl-1,3-diaminopropane and hexyloxypropyl-1,3-diaminopropane. The aldehyde scavengers described in EP 3310824 have the disadvantage that these low molecular weight amines often tend to have higher toxicity.

[0008] The object of the present invention was to provide polyurethanes, in particular polyurethane foams, which have improved emission behavior, in particular that of aldehydes, such as formaldehyde, and also have excellent emission behavior of further compounds, for example reduced nitrogen content and odor emissions.

[0009] The object of the present invention is to provide a method for the preparation of a polyisocyanate, comprising the steps of: (a) a polyisocyanate; (b) a polymeric compound having groups reactive towards isocyanates; (c) optionally a catalyst; (d) a polyisocyanate having the general formula H 2 NW-NR-[W-NR] l -[Q-NR] m -[S-NR] n -W-NH 2 and optionally (e) a blowing agent, (f) a chain extender and / or a crosslinker, and (g) an auxiliary and / or additive to form a reaction mixture, and reacting the reaction mixture to obtain a polyurethane, wherein each W independently represents a linear or branched hydrocarbon having 3 to 10 carbon atoms, each Q represents an ethylene residue, each S independently represents a substituted hydrocarbon, each R independently represents hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms, H represents a hydrogen atom, and N represents a nitrogen atom, l represents a value of 0 to 100, m represents a value of 0 to 50, and n represents a value of 0 to 100, wherein the polydispersity of the polymeric amine (d) is at least 1.2. The present invention further relates to polyurethanes which can be prepared by the process according to the invention, as well as the use of such polyurethanes in enclosed spaces, for example in vehicles, and to a process for the preparation of a polyurethane comprising (b) a polymeric compound having groups reactive towards isocyanates, (c) a catalyst and (d) a polymeric compound of the general formula H 2 NW-NR-[W-NR] l -[Q-NR] m -[S-NR] n -W-NH 2 and a blowing agent comprising water, wherein the polydispersity of said polymeric amine (d) is at least 1.2.

[0010] Polyurethanes in the sense of the present invention include all known polyisocyanate polyaddition products. These include addition products of isocyanates and alcohols as well as modified polyurethanes that may contain isocyanurate structures, allophanate structures, urea structures, carbodiimide structures, uretonimine structures, biuret structures and further isocyanate addition products. These polyurethanes according to the present invention include in particular solid polyisocyanate polyaddition products, such as thermosetting plastics, and foams based on polyisocyanate polyaddition products, such as flexible foams, semi-rigid foams, rigid foams or integral foams, as well as polyurethane coatings and binders. Preferably, the polyurethanes according to the present invention are polyurethane foams or solid polyurethanes, which do not contain further polymers in addition to the polyurethane building blocks (a) to (g) described below.

[0011] Within the scope of the present invention, polyurethane foams are understood to be foams according to DIN 7726. The polyurethane flexible foams according to the present invention have a compressive stress or compressive strength at 10% strain of less than or equal to 15 kPa, preferably from 1 to 14 kPa and in particular from 4 to 14 kPa, according to DIN 53 421 / DIN EN ISO 604. The polyurethane semi-rigid foams according to the present invention have a compressive stress at 10% strain of more than 15 kPa and less than 80 kPa, according to DIN 53 421 / DIN EN ISO 604. The polyurethane semi-rigid foams and polyurethane flexible foams according to the present invention preferably have an open cell content of more than 85%, particularly preferably more than 90%, according to DIN ISO 4590. Further details about the polyurethane flexible foams and polyurethane semi-rigid foams according to the present invention can be found in “Kunststoffhandbuch, Band 7, Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapter 5.

[0012] The polyurethane rigid foams according to the invention have a compressive stress at 10% strain of 80 kPa or more, preferably 120 kPa or more, particularly preferably 150 kPa or more. Furthermore, the polyurethane rigid foams have a closed cell content of more than 80%, preferably more than 90%, according to DIN ISO 4590. Further details about the polyurethane rigid foams according to the invention can be found in “Kunststoffhandbuch, Band 7, Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapter 6.

[0013] Elastomeric polyurethane foams are to be understood within the scope of the present invention as being polyurethane foams according to DIN 7726 which, after a short deformation of only 50% of their thickness, do not exhibit a permanent deformation of more than 2% of their starting thickness after 10 minutes according to DIN 53 577. They may be polyurethane rigid foams, polyurethane semi-rigid foams or polyurethane flexible foams.

[0014] Polyurethane integral foams are polyurethane foams according to DIN 7726 which, due to the molding method, have a surface layer with a higher density than the core. The total apparent density averaged over the core and the surface layer is then preferably greater than 100 g / L. Polyurethane integral foams in the sense of the present invention can also be polyurethane rigid foams, polyurethane semi-rigid foams or polyurethane flexible foams. Further details about the polyurethane integral foams according to the invention can be found in "Kunststoffhandbuch, Band 7, Polyurethane", Carl Hanser Verlag, 3rd edition, 1993, chapter 7.

[0015] In this case, the polyurethane according to the present invention is, in a preferred embodiment, a polyurethane foam having an average density of 10 to 850 g / L, preferably a polyurethane semi-rigid foam or a polyurethane flexible foam or a polyurethane rigid foam, particularly preferably an elastomeric polyurethane flexible foam, a polyurethane semi-rigid foam or an elastomeric polyurethane integral foam. The elastomeric polyurethane integral foam preferably has an average density of the core and the surface layer of 150 to 500 g / L. The polyurethane flexible foam preferably has an average density of 10 to 100 g / L. The polyurethane semi-rigid foam preferably has an average density of 70 to 150 g / L.

[0016] In a further preferred embodiment, the polyurethane is a solid polyurethane, preferably having a density of more than 850 g / L, preferably 900-1400 g / L and particularly preferably 1000-1300 g / L. In this case, the solid polyurethane is obtained without adding a blowing agent. Small amounts of blowing agent, for example water contained in the polyol due to production constraints, are not to be understood as adding a blowing agent within the scope of the present invention. Preferably, the reaction mixture for producing the dense polyurethane contains less than 0.2% by weight of water, particularly preferably less than 0.1% by weight and in particular less than 0.05% by weight.

[0017] In this case, the polyurethanes according to the invention are preferably used in the interior space of transport vehicles, for example ships, airplanes, trucks, cars or buses, particularly preferably cars or buses and especially cars.In this case, the interior space of the cars and buses is called automobile interior in the following.Polyurethane flexible foams can be used as seat cushion materials, polyurethane semi-rigid foams as foam backings for door side elements or instrument panels, polyurethane integral foams as steering wheels, gear knobs or headrests, and solid polyurethanes can be used, for example, as cable sheaths.

[0018] The polyisocyanate component (a) used for the preparation of polyurethanes according to the invention includes all polyisocyanates known for the preparation of polyurethanes. These include aliphatic, cycloaliphatic and aromatic di- or polyfunctional isocyanates known from the prior art, as well as any mixtures thereof. Examples are 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, mixtures of monomeric diphenylmethane diisocyanate with polynuclear homologues of said diphenylmethane diisocyanate (polymeric MDI), isophorone diisocyanate (IPDI) or its oligomers, 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate (TDI) or mixtures thereof, tetramethylene diisocyanate or its oligomers, hexamethylene diisocyanate (HDI) or its oligomers, naphthylene diisocyanate (NDI) or mixtures thereof.

[0019] Preferably, 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate (TDI) or mixtures thereof, monomeric diphenylmethane diisocyanate and / or polynuclear homologues of said diphenylmethane diisocyanate (polymeric MDI) and mixtures thereof are used. Further possible isocyanates are described, for example, in “Kunststoffhandbuch, Band 7, Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapters 3.2 and 3.3.2.

[0020] The polyisocyanate component (a) can be used in the form of a polyisocyanate prepolymer. These polyisocyanate prepolymers can be obtained by reacting an excess amount of the polyisocyanate (component (a-1)) with a polymer compound (b) (component (a-2)) having a group reactive with isocyanates and / or a chain extender (f) (component (a-3)) at a temperature of, for example, 30 to 100°C, preferably about 80°C, to obtain the isocyanate prepolymer.

[0021] The polymeric compounds (a-2) having groups reactive towards isocyanates and the chain extenders (a3) ​​are known to those skilled in the art and are described, for example, in "Kunststoffhandbuch, 7, Polyurethane", Carl Hanser-Verlag, 3rd Edition, 1993, Chapter 3.1. Thus, for example, as the polymeric compounds (a-2) having groups reactive towards isocyanates, it is also possible to use the polymeric compounds having groups reactive towards isocyanates described below under (b).

[0022] As the polymeric compound (b) having a group reactive towards isocyanates, any known compound having at least two hydrogen atoms reactive towards isocyanates can be used, for example those having a functionality of 2 to 8 and a number average molecular weight of 400 to 15000 g / mol. For example, compounds selected from the group of polyether polyols, polyester polyols or mixtures thereof can be used.

[0023] Polyetherols are prepared, for example, from epoxides, such as propylene oxide and / or ethylene oxide, or from tetrahydrofuran with hydrogen-active starter compounds, such as aliphatic alcohols, phenols, amines, carboxylic acids, water or compounds of natural origin, such as saccharose, sorbitol or mannitol, using catalysts, such as basic catalysts or double metal cyanide catalysts, which are described, for example, in PCT / EP2005 / 010124, EP 90444 or WO 05 / 090440.

[0024] Polyesterols are prepared, for example, from aliphatic or aromatic dicarboxylic acids and polyhydric alcohols, polythioether polyols, polyesteramides, hydroxyl-containing polyacetals and / or hydroxyl-containing aliphatic polycarbonates, preferably in the presence of an esterification catalyst. Further possible polyols are described, for example, in “Kunststoffhandbuch, Band 7, Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, Chapter 3.1.

[0025] In addition to the polyetherols and polyesterols described, filler-containing polyetherols or polyesterols, also called polymeric polyetherols or polymeric polyesterols, can be used. Such compounds preferably contain dispersed particles made of thermoplastics, for example olefinic monomers, such as acrylonitrile, styrene, (meth)acrylates, (meth)acrylic acid and / or acrylamide. Such filler-containing polyols are known and commercially available. Their preparation is described, for example, in DE 1 111 394, US 3 304 273, US 3 383 351, US 3 523 093, DE 1 152 536, DE 1 152 537, WO 2008 / 055952 and WO 2009 / 128279. Furthermore, as the polymer compound (b) having groups reactive towards isocyanates according to the present invention, at least one polyesterol can be used which is obtainable by polycondensation of an acid component and an alcohol component, where the acid component contains malonic acid and / or a derivative thereof and the alcohol component contains an aliphatic dialcohol having 4 to 12 carbon atoms, the preparation of which is described, for example, in WO 2019 / 149583.

[0026] In a particularly preferred embodiment of the present invention, said component (b) contains a polyetherol and more preferably does not contain a polyesterol.

[0027] General formula H 2 NW-NR-[W-NR] l -[Q-NR] m -[S-NR] n-W-NH 2 Due to the catalytic action of the compound (d) of the present invention, the use of an additional polyurethane catalyst can be reduced. If an additional catalyst (c) is used, any conventional polyurethane catalyst can be used. In this case, if used, the catalyst (c) preferably contains an incorporable amine catalyst, and particularly preferably, the catalyst (c) consists of an incorporable amine catalyst.

[0028] Typical catalysts which can be used in the preparation of said polyurethanes include, for example, amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo-(3,3,0)-octane, and preferably 1,4-diazabicyclo-(2,2,2)-octane, and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyldiethanolamine and N-ethyldiethanolamine and dimethylethanolamine. Likewise, organometallic compounds, preferably organotin compounds, such as tin(II) salts of organic carboxylic acids, such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate and tin(II) laurate, and dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, as well as bismuth carboxylates, such as bismuth(III) neodecanoate, bismuth-2-ethylhexanoate and bismuth octanoate or mixtures thereof, are worthy of consideration. The organometallic compounds can be used alone or, preferably, in combination with a strongly basic amine. When the component (b) is an ester, preferably exclusively amine catalysts are used.

[0029] The incorporable amine catalysts have at least one, preferably 1 to 8 and particularly preferably 1 to 2, groups reactive towards isocyanates, such as primary amino groups, secondary amino groups, hydroxyl groups, amide groups or urea groups, preferably primary amino groups, secondary amino groups, hydroxyl groups. Incorporable amine catalysts are mostly used for the production of low-emission polyurethanes, in particular for use in the automotive interior area. Such catalysts are known and are described, for example, in EP 1888664. They include compounds which, in addition to said one or more groups reactive towards isocyanates, preferably have one or more tertiary amino groups. Preferably, at least one of the tertiary amino groups of the incorporable catalysts has at least two aliphatic hydrocarbon residues, preferably 1 to 10 carbon atoms per residue, particularly preferably 1 to 6 carbon atoms per residue. Particularly preferably, the tertiary amino group has two residues independently selected from methyl and ethyl residues, as well as a further organic residue. Examples of usable incorpo- rable catalysts are bis(dimethylaminopropyl urea, bis(N,N-dimethylaminoethoxyethyl)carbamate, dimethylaminopropyl urea, N,N,N-trimethyl-N-hydroxyethyl bis(aminopropyl ether), N,N,N-trimethyl-N-hydroxyethyl bis(aminoethyl ether), diethylethanolamine, bis(N,N-dimethyl-3-aminopropyl)amine, 1-(3-aminopropyl)pyrrolidine, dimethylaminopropylamine, 3-dimethylaminopropyl-N,N-dimethylpropanol ... Pan-1,3-diamine, dimethyl-2-(2-aminoethoxyethanol), (1,3-bis(dimethylamino)-propan-2-ol), N,N-bis-(3-dimethylamino-propyl)-N-isopropanolamine, bis-(dimethylaminopropyl)-2-hydroxyethylamine, N,N,N-trimethyl-N-(3-aminopropyl)-bis(aminoethyl ether), 1,4-diazabicyclo[2.2.2]octane-2-methanol and 3-dimethylaminoisopropyl-diisopropanolamine or mixtures thereof.

[0030] If catalysts (c) are used, these can be used, for example, in a concentration of from 0.001 to 5% by weight, in particular from 0.05 to 2% by weight, of catalyst or catalyst combination, based on the total weight of component (b).

[0031] As the polymer amine (d), a compound represented by the general formula H 2 NW-NR-[W-NR] l -[Q-NR] m -[S-NR] n -W-NH 2 wherein the polydispersity of the polymeric amine (d) is at least 1.2, where H represents a hydrogen atom and N represents a nitrogen atom.

[0032] Each W independently represents a linear or branched hydrocarbon having 3 to 10 carbon atoms, preferably a propylene or butylene residue and especially a propylene residue.

[0033] Each Q represents an ethylene residue. Each S represents, independently of the others, a substituted hydrocarbon, for example an alkylene residue substituted with a halogen atom or an oxygen atom, or a cyclic residue. An example is the residue CH 2 -CH 2 -O-CH 2 -CH 2 -or expression [ka] is a residue of

[0034] Each R independently of the others represents hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms. Preferably, each R represents a hydrogen atom, a methyl residue, an ethyl residue or a propyl residue, particularly preferably a methyl residue or hydrogen. Particularly preferably, at least 50%, particularly preferably at least 75% and in particular 100% of the residues R represent hydrogen atoms.

[0035] The subscripts l and n stand for values ​​between 0 and 100, m between 0 and 50. The subscripts are preferably selected in such a way that the number-average molecular weight of the polymeric amine (d) is between 300 and 5000 g / mol, particularly preferably between 400 and 3000 g / mol and in particular between 600 and 1500 g / mol. Since the polymeric amine (d) has a molecular weight distribution, the values ​​of l, m and n are obtained by averaging and therefore may take fractional values. The number-average molecular weight can be determined, for example, by GPC. Within the scope of the present invention, the GPC measurements were carried out by a combination of three columns: HFIP-LG Guard, PL HFIPGEL and PL HFIPGel. The eluent was delivered at a constant flow rate of 1 mL / min with hexafluoroisopropanol and 0.05% by weight potassium trifluoroacetate. The sample to be injected was pumped through a prefilter Millipore Millex FG (0.2 μm). 50 μL were injected at a concentration of 1.5 mg / mL (diluted with eluent). The column effluent was measured at λ=230 and 280 nm with a UV detector DRI Agilent 1100. Calibration was carried out with PMMA standards (PSS, Mainz, Germany) having molar masses of 800 to 2.2 million g / mol. Values ​​outside the calibration range were extrapolated. The polydispersity calculated from the ratio of the weight-average and number-average molecular weights is then preferably at least 1.2, particularly preferably 1.3 to 10 and in particular 1.5 to 5.

[0036] In this case, the units -W-NR-, -Q-NR- and -S-NR- are H 2 As long as it is ensured that the NW- groups are present as terminal groups, they may be arranged in the molecule in any desired manner, for example alternating, block-like or statistical manner, preferably statistically.

[0037] Said polymeric amine (d) can be prepared by polyamination reaction. The primary amine that can be used as starting material for preparing said polymeric amine (d) preferably has a propyleneamine residue as an end group. In addition to the diamines having said propyleneamine groups, further primary diamines can be used. These include linear, branched or cyclic aliphatic diamines. Examples of such further diamines are ethylenediamine, butylenediamine (e.g. 1,4-butylenediamine or 1,2-butylenediamine), diaminopentane (e.g. 1,5-diaminopentane or 1,2-diaminopentane), diaminohexane (e.g. 1,6-diaminohexane, 1,2-diaminohexane or 1,5-diamino-2-methylpentane), diaminoheptane (e.g. 1,7-diaminoheptane or 1,2-diaminoheptane), diaminooctane (e.g. 1,8-diaminooctane or 1,2-diaminooctane), diaminononane (e.g. 1,9-diaminononane or 1,2-diaminononane), diaminodecane (e.g. 1,10-diaminodecane), diaminoundecane (e.g. 1,11-diaminoundecane or 1,2-diaminoundecane), diaminododecane (e.g. 1,12-diaminododecane or 1,2-diaminododecane), where the corresponding α,ω-diamines are preferred over their 1,2-isomers, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, isophoronediamine, 2,2-dimethylpropane-1,3-diamine, 4,7,10-trioxatridecane-1,13-diamine, 4,9-dioxadodecane-1,12-diamine, polyetheramines and 3-(methylamino)propylamine. Preference is given to 1,2-ethylenediamine and 1,4-butanediamine. In this case, the reaction is controlled so as to obtain propyleneamine residues, butyleneamine residues, pentyleneamine residues, hexyleneamine residues, heptyleneamine residues, octyleneamine residues, nonyleneamine residues and / or decyleneamine residues, preferably propyleneamine residues and / or butyleneamine residues, as end groups.This can be controlled, for example, by the order of addition of the starting compounds to the reaction mixture.

[0038] Suitable catalysts for the polytransamination reaction are especially heterogeneous catalysts comprising one or more transition metals selected from the group Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt, preferably from the group Co, Ni, Ru, Cu and Pd, particularly preferably from the group consisting of Co, Ni and Cu.

[0039] The polytransamination reaction is carried out in the presence of hydrogen, for example at a hydrogen partial pressure of 1-400 bar, preferably at 1-200 bar, and most preferably at 1-100 bar, and at a reactor temperature in the range of 50-200°C, preferably in the range of 90-180°C, and most preferably in the range of 130-170°C.

[0040] In a particularly preferred embodiment, the polymeric amine (d) according to the invention is obtainable by polyamination reaction of monomer (A), optionally monomer (B) and / or optionally monomer (C), where monomer (A) can be described by the following formula: [ka] Monomer (B) can be described by the formula: [ka] and the monomer (C) can be described by the formula: [ka] Here, k is 0 to 1, l is 1 to 3, m is 1 to 4, o is 0 to 1, and R represents a C1 to C18 alkyl chain.

[0041] Monomer (A) is N,N'-bis-(3-aminopropyl)ethylenediamine (N4-amine), obtained starting from the addition of about 2 equivalents of acrylonitrile to 1,3-propanediamine (1,3-PDA) either as a pure material or as a crude mixture, followed by reduction. Preferably, the N4-amine used has a purity of more than 80% by weight, particularly preferably more than 90% by weight and especially more than 97% by weight.

[0042] The key feature of monomer (A) is the secondary diamine disubstituted with a C2-spacer, which avoids cyclization to piperazine units in the form of 6- and 7-membered rings (e.g. piperazine or homopiperazine) during typical transamination conditions, thus allowing the formation of higher molecular weight polymers with high purity.

[0043] Examples of monomers (B) are 1,3-PDA ​​(m=1) and their oligomers, such as N1-(3-aminopropyl)-propane-1,3-diamine (m=2), N1,N1'-(propane-1,3-diyl)bis(propane-1,3-diamine) (m=3) and N1-(3-aminopropyl)-N3-(3-((3-aminopropyl)amino)propyl)-propane-1,3-diamine (m=4), or mixtures thereof. Particularly preferred is 1,3-PDA ​​as monomer (B).

[0044] An example of monomer (C) is N1-methylpropane-1,3-diamine (o=0, l=1, k=0, R=CH 3 ), N1-(3-aminopropyl)-N1-methylpropane-1,3-diamine (o=1, l=1, k=0, R=CH 3 ), N1-(3-aminopropyl)-N3-methylpropane-1,3-diamine (o=0, l=1, k=1, R=CH 3 ), N,N-bis(3-aminopropyl)methylamine (o=1, l=1, k=1, R=CH 3) and monomers with variations of o=0-1, l=1-3 and k=0-1, and mixtures thereof. The R group of the monomer (C) is a C1-C18 alkyl residue, preferably C1-C4, and most preferably methyl. Particularly preferably, the monomer (C) is N,N-bis(3-aminopropyl)methylamine (BAPMA).

[0045] For the preparation of the polymeric amine (d) according to the invention, preferably monomer (A), optionally monomer (B) and / or optionally monomer (C) are premixed in the form of solutions and conveyed into the reactor. Alternatively, monomer (A), optionally monomer (B) and / or optionally monomer (C), preferably also in the form of solutions, are pumped independently of one another and combined immediately before the reactor.

[0046] In this case, the compound (d) is preferably used in an amount of 0.001 to 5% by weight, particularly preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight, and especially 0.1 to 0.5% by weight, based on the weight of the component (b).

[0047] If the polyurethane according to the invention is present as a polyurethane foam, the reaction mixture according to the invention further contains a blowing agent (e). Any blowing agents known for the production of polyurethanes can be used here. These can include chemical and / or physical blowing agents. Such blowing agents are described, for example, in “Kunststoffhandbuch, Band 7, Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapter 3.4.5. Chemical blowing agents are understood to be compounds which form gaseous products by reaction with isocyanates. Examples of such blowing agents are water or carboxylic acids. Physical blowing agents are understood to be compounds which are dissolved or emulsified in the feedstocks for the polyurethane production and which evaporate under the conditions of the polyurethane formation. They are, for example, hydrocarbons, halogenated hydrocarbons and other compounds, such as perfluorinated alkanes, for example perfluorohexane, chlorofluorocarbons, and also ethers, esters, ketones, acetals and / or liquid carbon dioxide. The blowing agents can be used in any amount in each case. Preferably, the blowing agent is used in an amount such that the resulting polyurethane foam has a density of 10 to 850 g / L, particularly preferably 20 to 800 g / L and in particular 25 to 500 g / L. Particularly preferably, a blowing agent containing water is used.

[0048] As chain extenders and crosslinkers (f), compounds having at least two groups reactive with isocyanates and having a molecular weight of less than 400 g / mol can be used, where molecules having two hydrogen atoms reactive with isocyanates are called chain extenders, and molecules having more than two hydrogen atoms reactive with isocyanates are called crosslinkers.However, in this case, it is also possible to omit the chain extender or crosslinker.However, in order to change mechanical properties, such as hardness, the addition of a chain extender, crosslinker or optionally a mixture thereof may also prove to be advantageous.

[0049] When chain extenders and / or crosslinkers are used, they are usually used in an amount of 0.5 to 60% by weight, preferably 1 to 40% by weight and particularly preferably 1.5 to 20% by weight, respectively, based on the total weight of components (b) to (f).

[0050] If chain extenders and / or crosslinkers (f) are used, known chain extenders and / or crosslinkers can be used in the preparation of polyurethanes. These are preferably low molecular weight compounds with functional groups reactive towards isocyanates, such as glycerol, trimethylolpropane, glycols and diamines. Further possible low molecular weight chain extenders and / or crosslinkers are described, for example, in “Kunststoffhandbuch, Band 7, Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapters 3.2 and 3.3.2.

[0051] In addition, auxiliaries and / or additives (g) can be used. Any auxiliaries and additives known for the production of polyurethanes can be used. Examples include surface-active substances, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, flame retardants, antioxidants, hydrolysis protection agents, fungistatic and bacteriostatic substances. Such substances are known and are described, for example, in “Kunststoffhandbuch, Band 7, Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapters 3.4.4 and 3.4.6 to 3.4.11.

[0052] In particular, the combination of compound (d) and an antioxidant further reduces the emission of organic substances, such as aldehydes. Examples of antioxidants are phenolic substances, such as 2,6-di-tert-butyl-4-methylphenol, benzenepropanolic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 branched alkyl esters, amine antioxidants, such as N,N'-diisopropyl-p-phenylenediamine, thiosynergists, such as dilauryl-5-thiodipropionate, phosphites and phosphonites, such as triphenylphosphite, diphenylalkylphosphite, benzofuranones and indolinones, other antioxidants, such as O-, N- and S-benzyl compounds, triazine compounds, amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, esters of substituted and unsubstituted benzoic acid, nickel compounds and esters of β-thiodipropionic acid, or mixtures of two or more of these antioxidants. Such antioxidants are described, for example, in International Publication No. WO 2017 / 125291 (WO2017125291) and are commercially available, for example, under the trade names Irganox 1076, Irganox 245, Irganox 2000, Irganox E201 (vitamin E), Irganox 5057 or Irgafos 38.

[0053] In general, in the preparation of the polyurethanes according to the invention, the polyisocyanate (a), the polyol (b), the catalyst (c), the compound (d) and, if used, the blowing agent (e) and the chain extender (f) and / or crosslinker (g) are reacted in such amounts that the equivalent ratio of the NCO groups of the polyisocyanate (a) to the sum of the reactive hydrogen atoms of the components (b), (c), (d) and optionally (e), (f) and (g) is 0.75 to 1.5: 1, preferably 0.80 to 1.25: 1. If the cellular plastic contains at least partially isocyanurate groups, a ratio of the NCO groups of the polyisocyanate (a) to the sum of the reactive hydrogen atoms of the components (b), (c), (d) and optionally (e), (f) and (g) of 1.5 to 20: 1, preferably 1.5 to 8: 1, is usually used. A ratio of 1:1 then corresponds to an isocyanate index of 100. In a preferred embodiment, an isocyanate component containing a polyisocyanate (a) is reacted with a polyol component containing a polymeric compound (b) having groups reactive towards isocyanates, a catalyst (c), a polymeric amine (d) and a blowing agent (e). In a particularly preferred embodiment, the polyol component contains the blowing agent water.

[0054] The specific starting materials (a)-(g) for preparing the polyurethanes according to the invention only differ quantitatively and qualitatively when thermoplastic polyurethanes, flexible foams, semi-rigid foams, rigid foams or integral foams are prepared as polyurethanes according to the invention.Therefore, for example, no blowing agent is used for the preparation of solid polyurethanes, and for thermoplastic polyurethanes, strictly difunctional starting materials are mainly used.Furthermore, the elasticity and hardness of the polyurethanes according to the invention can be varied, for example, via the functionality and chain length of the higher molecular weight compounds having at least two reactive hydrogen atoms.Such variations are known to those skilled in the art.

[0055] Starting materials for the preparation of solid polyurethanes are described, for example, in EP 0989146 or EP 1460094, starting materials for the preparation of flexible foams are described in PCT / EP2005 / 010124 and EP 1529792, starting materials for the preparation of semi-rigid foams are described in “Kunststoffhandbuch, Band 7, Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapter 5.4, starting materials for the preparation of rigid foams are described in PCT / EP2005 / 010955 and starting materials for the preparation of integral foams are described in EP 364854, US 5,506,275. No. 5,506,275 or EP 897,402. The starting materials described in these documents are then each further added with the compound (d).

[0056] According to the method of the invention, the polyurethanes obtainable by the method of the invention are also the subject of the invention. The polyurethanes according to the invention are preferably used in closed spaces, for example in residential buildings, as thermal insulation materials, for example insulation materials for pipes and refrigerators, in furniture manufacturing, for example as decorative elements or seat cushion materials, as mattresses, and in the interior spaces of vehicles, for example in automobile interior spaces, for example as steering wheels, dashboards, door panels, carpet foam backings, acoustic foams, for example headliners, and headrests or gear knobs. In this case, the polyurethanes according to the invention, in particular, have a significantly reduced formaldehyde emission compared to reference products without additives, but also compared to additives for reducing aldehydes from the prior art. Furthermore, the polyurethanes according to the invention only emit very small amounts of volatile organic compounds (VOC) according to VDA 278 and VDA 277. Finally, the polyurethanes according to the invention show excellent aging behavior and heat resistance.

[0057] The invention will now be described with reference to examples. EXAMPLES

[0058] The following amines were used to prepare the amine additives A1 to A5: N,N'-bis-(3-aminopropyl)ethylenediamine (N4-amine) N,N-bis-(3-aminopropyl)methylamine (BAPMA) 1,3-Propylenediamine (1,3-PDA).

[0059] Amine additive A1: Synthesis of polyethylene / -propylene copolyamine (poly(N4-co-PDA) copolymer (A1) 1,3-PDA ​​premixed with N4-amine in a ratio of 3:1% by weight is continuously pumped together with 15 NL / h of hydrogen gas into a tubular reactor with a packing of fixed-bed catalyst made of metallic cobalt, an internal diameter of 10 mm and an internal thermowell of 3.17 mm. The reaction pressure is 50 bar and the reactor temperature is 175° C. The premixed starting materials are conveyed at a rate of 0.2 kg / Lcat×h. The desired product is obtained directly as a clear effluent without further workup steps. The product obtained has a weight-average molecular weight of 3250 g / mol.

[0060] Amine Additive A2: Synthesis of Polyethylene / -Propylene Copolyamine (Poly(N4-co-PDA) Copolymer (A2) 1,3-PDA ​​premixed with N4-amine in a ratio of 3:1% by weight is continuously pumped together with 15 NL / h of hydrogen gas into a tubular reactor with a packing of fixed-bed catalyst made of metallic cobalt, an internal diameter of 10 mm and an internal thermowell of 3.17 mm. The reaction pressure is 50 bar and the reactor temperature is 167° C. The premixed starting materials are conveyed at a rate of 0.3 kg / Lcat×h. The effluent is distilled at 50 mbar and 60° C. for 2 hours and the product is obtained as a clear effluent. The product obtained has a weight average molecular weight of 702 g / mol.

[0061] Synthesis of Amine Additive A3: Polyethylene / -Propylene Copolyamine (PolyN4-Polymer (A3) The N4-amine is continuously pumped together with 15 NL / h of hydrogen gas into a tubular reactor with a packing of fixed-bed catalyst made of metallic cobalt, an internal diameter of 10 mm and an internal thermowell of 3.17 mm. The reaction pressure is 50 bar and the reactor temperature is 170° C. The premixed starting materials are conveyed at a rate of 0.27 kg / Lcat×h. The desired product is obtained directly as a clear effluent without further workup steps. The product obtained has a weight-average molecular weight of 700 g / mol.

[0062] Amine additive A4: Synthesis of polypropylene / -2,5-bis(aminomethyl)tetrahydrofuran copolyamine (poly(PDA-co-2,5-bis(aminomethyl)tetrahydrofuran) copolymer (A4) 1,3-PDA ​​premixed with 2,5-bis(aminomethyl)tetrahydrofuran in a ratio of 3:1 wt.% is continuously pumped together with 15 NL / h of hydrogen gas into a tubular reactor with a packing of fixed-bed catalyst made of metallic cobalt, an internal diameter of 10 mm and an internal thermowell of 3.17 mm. The reaction pressure is 50 bar and the reactor temperature is 170° C. The premixed starting materials are conveyed at a rate of 0.28 kg / Lcat×h. The desired product is obtained directly as a clear effluent without further workup steps. The product obtained has a weight-average molecular weight of 1010 g / mol.

[0063] Amine additive A5: Synthesis of polyethylene / -propylene BAPMA-copolyamine (Poly(N4-co-PDA-co-BAPMA) copolymer (A5) 1,3-PDA ​​premixed with N4-amine and BAPMA in a ratio of 4:3:3 wt.% is continuously pumped together with 15 NL / h of hydrogen gas into a tubular reactor with a packing of fixed-bed catalyst made of metallic cobalt, an internal diameter of 10 mm and an internal thermowell of 3.17 mm. The reaction pressure is 50 bar and the reactor temperature is 170° C. The premixed starting materials are conveyed at a rate of 0.28 kg / Lcat×h. The desired product is obtained directly as a clear effluent without further workup steps. The product obtained has a weight-average molecular weight of 770 g / mol.

[0064] Amine Additive V1: Tri-n-propylenetetraamine (TPTA) Amine Additive V2: N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine) Amine additive V3: a mixture of 50% by weight of tri-n-propylenetetraamine and 50% by weight of N,N'-bis-(3-aminopropyl)ethylenediamine.

[0065] The following starting materials were used to prepare the polyurethane foam: Polyol 1: A glycerin initiated polyether polyol based on ethylene oxide and propylene oxide having an average OH number of 27 mg KOH / g, an average functionality of 2.5 and a propylene oxide content of 78 wt. % based on the total weight of the polyether.

[0066] Polyol 2: A glycerin initiated polyether polyol based on ethylene oxide and propylene oxide having an average OH number of 35 mg KOH / g, an average functionality of 2.7 and a propylene oxide content of 85 wt. % based on the total weight of polyether.

[0067] Polyol 3: A glycerin initiated polyether polyol based on ethylene oxide and propylene oxide having an average OH number of 42 mg KOH / g, an average functionality of 2.7 and a propylene oxide content of 25 wt. % based on the total weight of polyether.

[0068] Polyol 4: A polyester polyol formed from adipic acid, 1,4-butanediol, isophthalic acid and monoethylene glycol having an average OH number of 55 mg KOH / g.

[0069] TEOA Triethanolamine Isopur® SU-12021 Black paste from ISL-Chemie Emulsifier: Half ester of maleic acid-olefin copolymer Jeffcat® ZF10: An amine catalyst from Huntsman.

[0070] Isocyanate 1: Polymeric diphenylmethane diisocyanate (PMDI) with an NCO content of 31.5% by weight and an average functionality of 2.7.

[0071] Isocyanate 2: a prepolymer consisting of methylene diphenyl diisocyanate having an NCO content of 23% by weight and an average functionality of 2, dipropylene glycol and a polyether polyol having an average OH number of 250 mg KOH / g, a functionality of 2 and a propylene oxide content of 83% by weight based on the total weight of the polyether.

[0072] Isocyanate 3: A mixture of methylene diphenyl diisocyanate and the corresponding carbodiimide having an NCO content of 29.5% by weight and an average functionality of 2.2.

[0073] The polyol component was prepared by mixing the following ingredients: Polyol 1 50.0 parts by weight Polyol 2 34.3 parts by weight Polyol 3 2.0 parts by weight Polyol 4 6.0 parts by weight TEOA 0.5 parts by weight Emulsifier 0.5 parts by weight Isopur® SU-12021 0.5 parts by weight Water 2.9 parts by weight 0.3 parts by weight of Jeffcat® ZF10 Additives A1 to A5 or V1 to V3, 0.1 parts by weight.

[0074] The isocyanate component was prepared by mixing the following ingredients: Isocyanate 1 30.0 parts by weight Isocyanate 2 35.0 parts by weight Isocyanate 3 35.0 parts by weight.

[0075] The polyol component and the isocyanate component were mixed with each other with an isocyanate index of 100 and added into a closed mold, resulting in a molded article with an average density of 120 g / L. The molded article was packaged in an airtight light-proof package immediately after production and stored at 25° C. for 3 to 10 days after production until the measurement of the emission amount. In the case of the obtained polyurethane semi-rigid foams, hereinafter referred to as Examples 1 to 5 and Comparative Examples 1 to 3, the emission amount values ​​were subsequently measured as follows: To measure formaldehyde and acetaldehyde, a method similar to ASTM D-5116-06 was used. The chamber size was 4.7 liters. As polyurethane samples, test pieces with a size of 110 mm x 100 mm x 25 mm from the inside of the foam were used. The temperature in the measurement chamber was 65°C during the measurement, and the relative air humidity was 50%. The air exchange rate was 3.0 liters per hour. The exhaust gas stream with volatile aldehydes from the polyurethane was passed through a cartridge with silica coated with 2,4-dinitrophenylhydrazine (DNPH) for 120 minutes. The DNPH cartridge was subsequently eluted with a mixture of acetonitrile and water. The concentrations of formaldehyde and acetaldehyde in the eluate were measured using HPLC-UV-Vis. With this configuration, the detection limit (NG) of formaldehyde emission was 5 μg / m 3 and acetaldehyde emission is 6μg / m 3 The following is the result.

[0076] Table 1: Formaldehyde and acetaldehyde emissions, as well as VOC and FOG emissions (measured according to VDA 278) from the semi-rigid foams when each additive A1-A5, and V1-V2 is added at the concentrations indicated, measured in the chamber, each reported in weight % of mixture A above.

[0077] Table 1 [Table 1]

[0078] Table 1 shows that the use of additives A1 to A5 according to the invention in mixture A significantly reduces the formaldehyde emission and the acetaldehyde emission remains unchanged or is slightly reduced. Additives V1 to V3 certainly also lead to a reduction in the formaldehyde emission, but also to an increase in the acetaldehyde emission.

[0079] Table 2: VOC and FOG emissions (measured according to VDA 278) of semi-rigid foams when each additive A5, V1 to V3 is added at the indicated concentrations, each reported in wt. % of mixture A above.

[0080] Table 2 [Table 2]

[0081] Table 2 shows that the use of the additive according to the invention in Mixture A reduces VOC as well as FOG emissions below the levels of the corresponding foams with additives V1-V3.

Claims

1. A method for producing polyurethane, comprising: (a) a polyisocyanate, (b) a polymer compound having a group reactive with isocyanate, (c) optionally a catalyst, (d) a polymer amine of the general formula H ２ N-W-NR-[W-NR] ｌ -[Q-NR] ｍ -[S-NR] ｎ -W-NH ２ and optionally (e) a blowing agent, (f) a chain extender and / or a crosslinking agent and (g) an auxiliary agent and / or an additive are mixed to form a reaction mixture, and the reaction mixture is reacted to obtain polyurethane, wherein, each W independently represents a linear or branched hydrocarbon having 3 to 10 carbon atoms, each Q represents an ethylene residue, each S independently represents a substituted hydrocarbon, each R independently represents hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms, H represents a hydrogen atom, and N represents a nitrogen atom, l represents a value from 0 to 100, m represents a value from 0 to 50, and n represents a value from 0 to 100, wherein the polydispersity of the polymer amine (d) is at least 1.

2.

2. The method according to claim 1, wherein W represents propylene or butylene.

3. The method according to claim 1 or 2, wherein the number average molecular weight of the polymer amine (d), determined by GPC, is 300 to 5000 g / mol. **Claim 4**: The method according to claim 1 or 2, characterized in that 50 to 100% of the residue R represents hydrogen. **Claim 5** The method according to claim 1 or 2, characterized in that the polymer compound (b) having a group reactive with the isocyanate contains a polyether polyol. **Claim 6** The method according to claim 1 or 2, characterized in that the catalyst (c) contains an incorporable amine catalyst. **Claim 7** The method according to claim 6, characterized in that a compound having one or more aliphatic tertiary amino groups in addition to a group reactive with one or more isocyanates is used as the incorporable catalyst. **Claim 8** The method according to claim 7, characterized in that at least one tertiary amino group of the incorporable catalyst has two residues independently selected from methyl and ethyl residues, and a further organic residue. **Claim 9** The method according to claim 1 or 2, characterized in that the polyurethane is a polyurethane foam having an average density of 10 to 850 g / L. **Claim 10** The method according to claim 1 or 2, characterized in that the polyurethane is a dense polyurethane having an average density of more than 850 g / L. **Claim 11** The method according to claim 1 or 2, characterized in that the polyurethane is a member of a mattress or furniture. **Claim 12** A polyurethane that can be produced by the method according to claim 1 or 2. **Claim 13** Use of the polyurethane according to claim 12 in a closed space. **Claim 14** (b) A polymer compound having a group reactive with an isocyanate, (c) a catalyst, and (d) the general formula H ２N-W-NR-[W-NR] ｌ -[Q-NR] ｍ -[S-NR] ｎ -W-NH ２ A polymer amine of the formula: [wherein each W independently represents a linear or branched hydrocarbon having 3 to 10 carbon atoms, each Q represents an ethylene residue, each S independently represents a substituted hydrocarbon, each R independently represents hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms, H represents a hydrogen atom, N represents a nitrogen atom, l represents a value from 0 to 20, m represents a value from 0 to 10, and n represents a value from 0 to 20], and a blowing agent containing water, wherein the polydispersity of the polymer amine (d) is at least 1.2, a composition.